title: Solvent-dependent reversible ligand exchange in nickel complexes of a monosulfide bis(diphenylphosphino)(N-thioether)amine.
abstract: The coordination chemistry of the DPPA-type functional phosphine bis(diphenylphosphino)(N-thioether)amine N(PPh2)2(CH2)3SMe () and its monosulfide derivative, (Ph2P)N{P(S)Ph2}(CH2)3SMe (1·S), towards Ni(II) precursors has been investigated. The crystal structures of N{P(S)Ph2}2(CH2)3SMe (1·S2), [NiCl2{(Ph2P)2N(CH2)3SMe-P,P}] (2), [NiCl2((Ph2P)N{P(S)Ph2}(CH2)3SMe-P,S)] (3), [Ni((Ph2P)N{P(S)Ph2}(CH2)3SMe-P,S)2]NiCl4 (3'), [Ni((Ph2P)N{P(S)Ph2}(CH2)3SMe-P,S)2](BF4)2 (4), and [Ni((Ph2P)NH{P(S)Ph2}-P,S)2]Cl2 (5) have been determined by single-crystal X-ray diffraction. In all of the complexes with the hybrid ligand 1·S, P,S-chelation to the Ni(II) center is observed. Despite the stability generally associated with five-membered ring chelation, easy migration of this LL'-type P,S-chelating ligand from one metal center to another was observed, which accounts for the reversible ligand-redistribution reaction occurring in the equilibrium between the neutral, diamagnetic complex [NiCl2LL'] and the paramagnetic ion-pair [Ni(LL')2][NiCl4]. Detailed investigations by multinuclear NMR, UV/Vis, and FTIR spectroscopic methods and DFT calculations are reported. Each of the formula isomers 3 and 3' can be selectively obtained, depending on the experimental conditions.
authors.affiliation: Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, 67081 Strasbourg, France.
authors.forename: Alessio
authors.initials: A
authors.lastname: Ghisolfi
authors.forename: Christophe
authors.initials: C
authors.lastname: Fliedel
authors.forename: Vitor
authors.initials: V
authors.lastname: Rosa
authors.forename: Roberto
authors.initials: R
authors.lastname: Pattacini
authors.forename: Aurore
authors.initials: A
authors.lastname: Thibon
authors.forename: Kirill Yu
authors.initials: KY
authors.lastname: Monakhov
authors.forename: Pierre
authors.initials: P
authors.lastname: Braunstein
mesh_terms: D000814:Aniline Compounds / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008024:Ligands; D008968:Molecular Conformation; D009532:Nickel / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry*; D013440:Sulfides / Q000737:chemistry
chemical_list: D000814:Aniline Compounds; D056831:Coordination Complexes; D008024:Ligands; D010720:Phosphines; D012997:Solvents; D013440:Sulfides; C581478:bis(diphenylphosphino)amine; D009532:Nickel
keywords: chelates; ligand exchange; nickel; short-bite ligands; solvent effects